TOPIC 8.

CHEMICAL CALCULATIONS II:

% composition, empirical formulas.
Percentage composition of elements in compounds.
In Topic 1 it was stated that a given compound always has the same composition
by weight regardless of how it was produced. The reason for this is that each
compound has a fixed chemical formula which specifies the number of atoms of
each of its component elements. For example, the compound glucose of formula
C6H12O6 always has 6 C atoms, 12 H atoms and 6 O atoms in every one of its
molecules. Using the mole concept, if the formula of the compound is known, then
from the atomic weights of the component elements, the % by weight for each
element in the compound can be calculated.
Using glucose as an example,
Molecular formula:

C 6H 12O 6.

Each glucose molecule contains:

6 carbon atoms

12 hydrogen atoms

6 oxygen atoms

an Avogadro number of glucose molecules (1 mole of glucose) contains

6 Avogadro number (= 6 moles) of C atoms and
12 Avogadro number (= 12 moles) of H atoms and
6 Avogadro number (= 6 moles) of O atoms.
1 mole of glucose has a mass (its gram formula weight or molar mass) which is the
sum of the gram atomic weights of all of the constituent atoms.
i.e. mass of 1 mole of glucose, C 6H 12O 6 = (6 12.01 + 12 1.01 + 6 16.00) g
= 180.18 g (using atomic weight data to 2 decimals)
1 mole of carbon atoms weighs 12.01 g and there are 6 moles of C atoms in 1 mole
of glucose, so the mass of carbon in 1 mole of glucose = 6 12.01 g = 72.06 g.
and % carbon in C6H12O6 = 72.06 100 % = 40.0 % by mass.
180.18
Similarly, the percentage of hydrogen and oxygen can be calculated as follows:
1 mole of H atoms weighs 1.01 g and there are 12 moles of H atoms in 1 mole of
glucose, so the mass of hydrogen in 1 mole of glucose = 12 1.01 g = 12.12 g.
% hydrogen = 12.12 100 % = 6.7 % by mass.
180.18
1 mole of O atoms weighs 16.00 g and there are 6 moles of O atoms in 1 mole of
glucose, so the mass of oxygen in 1 mole of glucose = 6 16.00 g = 96.00 g.
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% oxygen =

96.00 100 % = 53.3 % by mass.

180.18
[Note that the sum of the % of all the elements must add up to 100 %.]
Thus the % composition of glucose by mass is
carbon 40.0 %

oxygen 53.3 %

hydrogen 6.7 %

In this way, the % composition by mass of any compound can be calculated

provided that its formula is known.
Example: Calculate the % composition by mass of chloride ion in sodium chloride.
The molar mass of NaCl = 22.99 + 35.45 g = 58.44 g.
From the formula of sodium chloride,
1 mole of NaCl (58.44 g) contains 1 mole of Cl (35.45 g).
Therefore % by mass of Cl = 35.45 100 % = 60.67 %
58.44
Determination of empirical formulas of compounds.
Recall that the empirical formula of a compound is the simplest integer ratio of the
elements in that compound. The empirical formula of any pure compound can be
determined from analytical data giving the percentage composition by mass of the
elements present. The calculations involved are simply the reverse of those just
done above where, from the empirical or molecular formula, the % by weight of its
component elements was deduced. Now, given the % by weight of the component
elements, the empirical formula will be deduced. This is best shown by some
examples.
Example 1. Analysis of a compound returns the following data for % by mass:
iron (Fe): 63.5 %

sulfur (S): 36.5 %

From the data, in 100.0 g of compound there would be 63.5 g of iron combined
with 36.5 g of sulfur. The empirical formula expresses the simplest ratio of the
relative number of atoms of Fe and S present and as one mole of atoms of any
element contains N A atoms of that element, this will be the same as the relative
number of moles of Fe and S atoms present in the compound. To calculate the
number of moles of Fe and of S atoms present in the compound, divide the mass of
each of these two constituent elements by their atomic weights.
Moles of Fe = mass / atomic weight of Fe = 63.5/55.85 = 1.14 mole of Fe atoms
Moles of S = mass / atomic weight of S = 36.5/32.07 = 1.14 mole of S atoms
Thus the ratio of moles of Fe to moles of S in the compound is
1.14 moles of Fe atoms : 1.14 moles of S atoms.
i.e. 1.14 NA Fe atoms: 1.14 N A S atoms which on dividing by N A gives
1.14 Fe atoms:1.14 S atoms.
However, the empirical formula must have integer quantities for all the numbers of
atoms in it. In this example, it is obvious that, within the usual allowable
experimental error in analytical data of about 0.3 %,
ratio of atoms of Fe : atoms of S = 1.00 : 1.00 and the empirical formula is FeS.

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The above calculation is illustrated in the following flow diagram.

iron 63.5 % by mass

sulfur 36.5 % by mass

= 63.5 g in 100 g of compound

= 36.5 g in 100 g of compound

Calculate moles of Fe and S atoms:

63.5 / 55.85 moles of Fe atoms

36.5 / 32.07 moles of S atoms

= 1.14 moles Fe

= 1.14 moles S
As ratio of moles =
ratio of atoms,
Fe1.14S1.14
Simplify:

FeS
Example 2. Analysis returns the following data for an unknown compound:
nitrogen: 26.2 %

chlorine: 66.4 %

hydrogen: 7.5 %

by mass.

Determine its empirical formula.

[Note that these percentages add up to 100 %, within the experimental error. If
they do not add up to 100 %, the difference is attributed to oxygen for which
normally there is no analytical data available.]
In 100.0 g of compound there are 26.2 g of nitrogen, 66.4 g of chlorine and 7.5 g
of hydrogen.
To convert to moles of N, Cl and H atoms, divide each mass by the atomic weight
of each element. [A common error is to divide by the molecular weight for species
such as N, Cl, O and H which occur in nature as diatomic molecules.]
Moles of N atoms

= 26.2/14.01 = 1.87 mole of N atoms

Moles of Cl atoms = 66.4/35.45 = 1.87 mole of Cl atoms

Moles of H atoms = 7.5/1.008

= 7.4 mole of H atoms

ratio of the number of atoms of N : Cl : H in the compound is 1.87 : 1.87 : 7.4

This time, in order to convert these numbers to integers they must be divided by the
highest common factor. A good starting point is to divide each by the smallest
number, in this case 1.87.

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This provides N : Cl : H = 1.00 : 1.00 : 4.0

Thus the empirical formula is NClH 4.
Molecular formulas.
In an earlier Topic, the molecular formula was shown to be a simple multiple of the
empirical formula. Once the empirical formula has been deduced, the molecular
formula for a compound that exists as molecules can be determined provided that
the molecular weight which can also be obtained by experiment is known.
Dividing the molecular weight by the empirical formula weight gives the integer by
which the empirical formula must be multiplied to obtain the molecular formula.
This is illustrated in the next example which also includes the situation where the
total of the percentage compositions does not add up to 100 %.
Example 3. An unknown compound whose molecular weight has been determined
to be 120 provided the following analytical results:
carbon: 40.0 %

hydrogen: 6.7 %

Determine the empirical and molecular formulas for this compound.

As the total % composition data given = 46.7 %, it is assumed that the balance of
the mass is oxygen = (100 46.7) % = 53.3 %.
In 100.0 g of compound there would be 40.0 g of carbon, 6.7 g of hydrogen and
53.3 g of oxygen atoms in combination.
The amount of each element present expressed as moles of atoms would be
C =

40.0
= 3.33 mole of C atoms
12.01
H = 6.7
= 6.6 mole of H atoms
1.008
O = 53.3
= 3.33 mole of O atoms
16.00
Therefore the ratio of atoms of C : H : O = 3.33 : 6.6 : 3.33
Dividing each by 3.33, the empirical formula is CH 2O.
The empirical formula weight of CH 2O = 12.01 + 2 1.008 + 16.00 = 30.
As the experimentally determined molecular weight is 120, then the empirical
formula must be multiplied by 120/30 = 4 to obtain the molecular formula.
i.e. the molecular formula is C4H8O4.
[Note the use of the word "amount" in these examples. By definition, "amount" is a
measure of the quantity of a given substance expressed in moles. This could be
compared with, say, "mass" which is a measure of quantity expressed for example
in grams, or "time" which is measured for example in seconds]

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Test your understanding of this section.

Why arent the percentages by mass of the constituent elements in a compound
related as simple integers?
In determining the empirical formula for a compound containing hydrogen, why
is the mass of hydrogen present divided by its atomic weight rather than its
molecular weight?
What information is needed in order to deduce the molecular formula of a
compound?
Objectives of this Topic.
When you have completed this Topic, including the tutorial questions, you should
have achieved the following goals:
1.

Understand the basis for calculating the percentage composition of

compounds from their molecular formulas and the reverse process, the
deduction of molecular formulas from experimentally obtained percentage
composition data.

2.

Be able to calculate the percentage composition by mass of any compound

from its formula.

3.

Be able to calculate the empirical formula of a compound from the

experimentally derived percentage composition by mass data.

4.

Be able to determine the molecular formula for a compound from its

empirical formula and its molecular weight.
SUMMARY

The formula for any given compound always has the same number of atoms of
each of its constituent elements combined in simple integer ratios. As the atoms of
each element always have their own characteristic mass, then it follows that any
given compound always has the same percentage composition of each element by
mass although, as seen in Topic 7, the masses of each element in the compound are
not in simple numerical ratios. Thus for any compound whose empirical formula is
known, the percentage composition by mass of each of its constituent elements can
be deduced.
Using this process in reverse, if the percentage composition of a compound is
available from experiment, then the empirical formula for the compound can be
deduced by converting this mass data into relative numbers of moles of each
element in the compound. This is done by dividing the mass of each element
present in a given mass of compound by that elements gram atomic weigh. The
relative number of moles of each element in the compound is the same as the
relative number of atoms of each, which when reduced to the simplest integer ratio,
is the empirical formula of the compound.
For molecular compounds, the molecular formula is a simple multiple of the
empirical formula. If the molecular weight is also available from experiment, then
the molecular formula can be deduced by comparing the empirical formula weight
with the molecular weight to obtain the required multiple.

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TUTORIAL QUESTIONS - TOPIC 8.

1. Determine the percentage by mass of:
(i)

bromide ion in potassium bromide

(ii)

carbon in carbon dioxide

(iii)

sulfur in lead(II) sulfate

(iv)

hydrogen in methane (CH4)

(v)

hydrogen in ethane (C2H6).

(vi)

carbon in carbon monoxide

(vii)

oxide ion in copper(I) oxide

(viii) oxide ion in copper(II) oxide

2.

(i) A compound of molar mass 62 g mol!1 contains C, H and O only.

Analysis gives 38.7 % carbon and 9.8 % hydrogen by mass.
Determine (a) the empirical and (b) the molecular formula of the compound.
(ii) A compound is found to contain the following weight percentages of
each element:
carbon = 52.1 %, hydrogen = 4.4 %, boron = 7.8 %, nitrogen = 10.1 %,
chlorine = 25.6 %.
What is the empirical formula of the compound?
(iii) (a) What is the empirical formula of a compound containing 40 % sulfur
and 60 % oxygen by weight?
(b) What is its molecular formula if its molecular weight is 240?
(iv) Derive the empirical formulas of substances having the following
percentage compositions by weight:
(a) Iron 63.5 %; sulfur 36.5 %
(b) Iron 46.5 %; sulfur 53.4 %
(c) Iron 53.7 %; sulfur 46.3 %
(v) A compound is shown to be ionic as it is soluble in water, providing a
solution that conducts electricity. Analysis of the compound gave the
following percentage composition by weight:
sodium = 32.4 %; sulfur = 22.6 %; oxygen (by difference) = 45.0 %.
Derive the empirical formula for this compound.
(vi) A gas formed by the reaction of N 2F 4 and S 2O 6F 2, is found to contain
nitrogen 9.5 %, sulfur 20.9 %, and fluorine 38.0 %;
The remainder was assumed to be oxygen.
What is the empirical formula of the gas?

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3. An iron supplement is used to treat anaemia and 50 mg (i.e. 50 10!3 g) of Fe2+

is required per tablet. If the iron compound used in the tablet is FeSO 4.6H 2O, what
mass of this compound would be required per tablet to provide the desired mass of
Fe2+?
4. [For those who fancy a challenge.]
The Law of Multiple Proportions states: "If two elements combine to form two or
more compounds, the various weights of one element which combine with a fixed
weight of the other element are in a simple ratio of whole numbers."
The five oxides of nitrogen contain respectively, 63.64 %, 46.67 %, 36.84 %,
30.44 % and 25.93 % by weight of nitrogen. Show that these numbers are in
accord with the above law.

ANSWERS TO TUTORIAL TOPIC 8

1.

(i)

67.14 %

(ii)

27.29 %

(iii)

10.57 %

(iv)

25.13 %

(v)

20.11 %

(vi)

42.88 %

(vii)

11.19 %

(viii) 20.11 %
Explanations and Partial Solutions.
(i) Molar mass of KBr = 119.0 g mol1
Molar mass of Br = 79.90 g mol1
There is only one Br in the formula for potassium bromide,
% Br in KBr = (79.90 / 119.0) 100 = 67.14 %
Note the importance of having the correct formula for the compound, potassium
bromide.
(ii) Molar mass of CO 2 = 44.01g mol1
(iii) Molar mass of PbSO 4 = 303.3 g mol1
(iv) Molar mass of CH 4 = 16.04 g mol1
Molar mass of H = 1.008 g mol1
There are four H atoms in each CH 4 molecule,
% H in methane = [(4 1.008) / 16.04] 100 = 25.13 %
(v) Molar mass of C 2H 6 = 30.07 g mol1
(vi) Molar mass of CO = 28.01 g mol1

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(vii) Molar mass of Cu 2O = 143.1 g mol1

(viii) Molar mass of CuO = 79.55 g mol1
2.

(i)

(a) CH 3O

(b) C 2H 6O 2

Worked Solution.
In 100 g compound, mass of carbon = 38.7 g, mass of hydrogen = 9.8 g and mass
of oxygen = (100.0 38.7 9.8) = 51.5 g.
Moles of C atoms = 38.7 / 12.01 = 3.22 mol
Moles of H atoms = 9.8 / 1.008 = 9.72 mol [Note the use of the atomic weight for
H as it is the number of moles of H atoms that is required.]
Moles of O atoms = 51.5 / 16.00 = 3.22 mol [Likewise, the atomic weight of O is
used so that moles of O atoms is obtained]
ratio of moles of C:H:O = 3.22 : 9.72 : 3.22 = ratio of atoms of C:H:O
Reducing these ratios to integers gives the empirical formula with the ratios of
C:H:O = 1.00 : 3.02 : 1.00, which within the allowable error for analysis (0.3%),
is CH3O
The formula mass of CH 3O = 12.01 + 3 1.008 + 16.00 = 31.0
Molar mass of the compound is 62 which corresponds to twice the empirical
formula mass. molecular formula is C 2H 6O 2.

3.

(ii)

C6H6BNCl

(iii)

(a) SO3

(b) S3O 9

(iv)

(a) FeS

(b) FeS2

(v)

Na2SO 4

(vi)

NSF3O3

(c) Fe2S3

0.23 g

Worked Solution.
One mole of FeSO4.6H2O contains one mole of Fe2+.
moles of FeSO 4.6H 2O = moles of Fe2+ required.
Moles Fe2+ = 50 103 / 55.85 = 8.95 104 mol.
Molar mass of FeSO 4.6H 2O = 260.0 g mol1.
Mass of FeSO4.6H2O required = 8.95 104 260.0 = 0.23 g.

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4. Take an amount of each compound such that there would be exactly 1.0 g of
nitrogen present in each sample. For each compound, calculate the mass of
compound taken and thence by difference, the mass of oxygen present.
If 63.64 % is nitrogen, then mass of compound = 100 1.0 g = 1.57 g
63.64
and mass of oxygen = 1.57 ! 1.0 = 0.57 g
If 46.67 % is nitrogen, then mass of compound = 100 1.0 g = 2.14 g
46.67
and mass of oxygen = 2.14 ! 1.0 = 1.14 g
If 36.84 % is nitrogen, then mass of compound = 100 1.0 g = 2.71 g
36.84
and mass of oxygen = 2.71 ! 1.0 = 1.71 g
If 30.44 % is nitrogen, then mass of compound = 100 1.0 g = 3.29 g
30.44
and mass of oxygen = 3.29 ! 1.0 = 2.29 g
If 25.93 % is nitrogen, then mass of compound = 100 1.0 g = 3.86 g
25.93
and mass of oxygen = 3.86 ! 1.0 = 2.86 g
Thus the ratios of N:O in the various compounds are
0.57 : 1.14 : 1.71 : 2.29 : 2.86
which simplifies to
1:2:3:4:5